The present invention relates to a process for preparing novel polyolefins. More particularly, the present invention is concerned with a process for preparing polyolefins of good particles having a large average particle diameter and a narrow molecular weight distribution, which process is capable of greatly increasing the polymer yield per solid and that per transition metal, thereby permitting the omission of the step of removing catalyst remaining in the resulting polymer, further capable of increasing the bulk density of the polymer and decreasing a fine particulate portion of the polymer.
Heretofore, in this technical field there have been known many catalysts comprising inorganic magnesium solids as carriers such as magnesium halide, magnesium oxide and magnesium hydroxide and a transition metal compound such as a titanium compound or a vanadium compound supported on the carriers. However, the polyolefins obtained in the prior art are generally low in bulk density, relatively small in average particle diameter and generally wide in particle size distribution so contain a large proportion of fine particles. Besides, when these powdery polymers are subjected to forming, there arise problems such as dusting and lowering of the forming, efficiency. For the reason, improvement has keenly been desired from the standpoint of productivity and polymer handling. Further, still further improvements are considered necessary in order to satisfy the recent keen desire for omitting the pelletizing step and using a powdery polymer directly in a processing machine.
The present inventors have previously found out a novel catalyst component with the above drawbacks remedied and already filed patent applications thereon (see Japanese Patent Publication Nos. 11651/1989 and 12289/1989 and Japanese Patent Laid Open Nos. 149605/1985, 32105/1987 and 207306/1987). The use of this catalyst component can afford a polymer having a high bulk density and a large average particle diameter. However, a further improvement has been considered necessary for omitting the pelletizing step and using a powdery polymer directly in a processing machine.
The present inventors have also proposed a catalyst capable of affording a polymer having a narrow molecular weight distribution and a reduced proportion of low molecular weight components, which is required particularly in the film field (see Japanese Patent Application No. 200348/1989). However, this polymer still cannot be considered satisfactory.
Having made extensive studies for the purpose of remedying such drawbacks and obtaining in an extremely high activity a polymer having a high bulk density, a narrow particle size distribution, an extremely small proportion of fine particles and a narrow molecular weight distribution, the present inventors accomplished the present invention.
More specifically, the present invention resides in a process for preparing a polyolefin by polymerizing or copolymerizing an olefin or olefins in the presence of a catalyst comprising a solid catalyst component and an organometallic compound, the solid catalyst component being prepared by the reaction of the following components [I], [II] and [III]:
[I] a reaction product obtained by the following components (1), (2) and (3) in the presence of a compound represented by the general formula R2OH wherein R2 is a hydrocarbon radical having 1 to 20 carbon atoms or an organic residue containing such an element as oxygen, nitrogen, sulfur, or chlorine:
(1) a silicon oxide and/or an aluminum oxide;
(2) a reaction product obtained by reacting a magnesium halide and a compound represented by the general formula [Me(OR)nXz-n] wherein Me represents an element of Groups I to IV in the Periodic Table, z represents the valence of the element Me, n is 0 less than nxe2x89xa6z, X is a halogen atom, and R is a hydrocarbon residue having 1 to 20 carbon atoms; and
(3) a titanium compound represented by the general formula Ti(OR1)mX4-m wherein R1 is a hydrocarbon radical having 1 to 20 carbon atoms, X is a halogen atom, and m is 0xe2x89xa6mxe2x89xa64;
[II] an organoaluminum compound represented by the general formula Al(OR3)pR4qX3-(p+q) wherein R3 and R4, which may be the same or different, are each a hydrocarbon residue having 1 to 24 carbon atoms, X is a halogen atom or hydrogen atom, and p and q are 0xe2x89xa6p less than 3, and 0xe2x89xa6qxe2x89xa63, provided 0 less than p+qxe2x89xa63; and
[III] a silicon compound represented by the general formula [R5aR6bR7cSi(OR8)dX4-(a+b+c+d)] where R5, R6, R7 and R8, which may be the same or different, are each a hydrocarbon residue having 1 to 20 carbon atoms, X is a halogen atom, and a, b, c and d are 0xe2x89xa6a less than 4, 0xe2x89xa6b less than 4, 0xe2x89xa6c less than 4 and 0 less than dxe2x89xa64, provided 0 less than a+b+c+dxe2x89xa64.
By the process of the present invention there is obtained, in extremely high activity, a polyolefin having a relatively large average particle diameter, a narrow particle size distribution, a reduced proportion of fine particles and a narrow molecular weight distribution. Besides, the bulk density and free fluidity of the polyolefin are high. These characteristics are very advantageous to the polymerization operation.
Further, the polyolefin prepared by the process of the present invention can be subjected to forming not only as pellets but also in the form of powder, without causing any trouble.
It is also a characteristic feature of the present invention that the polymer obtained using the catalyst specified in the present invention is extremely narrow in its molecular weight distribution and small in the amount thereof extracted in hexane, and that the amount of low grade polymers by-produced is very small. Therefore, when film is formed using the polyolefin of a narrow molecular weight distribution prepared by the process of the present invention, it has a lot of merits, for example, high strength and transparency, superior anti-blocking property and heat-sealability.
The present invention will be described concretely hereinunder.
The catalyst used in the polyolefin preparing process of the present invention comprises a solid catalyst component and an organometallic compound, the said solid catalyst component being prepared from the following components [I], [II] and [III]:
[I] a reaction product obtained by the following components (1), (2) and (3) in the presence of a compound represented by the general formula R2OH wherein R2 is a hydrocarbon radical having 1 to 20 carbon atoms or an organic residue containing such an element as oxygen, nitrogen, sulfur, or chlorine:
(1) a silicon oxide and/or an aluminum oxide;
(2) a reaction product obtained by reacting a magnesium halide and a compound represented by the general formula [Me(OR)nXz-n] wherein Me represents an element of Groups I to IV in the Periodic Table, z represents the valence of the element Me, n is 0 less than nxe2x89xa6z, X is a halogen atom, and R is a hydrocarbon residue having 1 to 20 carbon atoms; and
(3) a titanium compound represented by the general formula Ti(OR1)mX4-m wherein R1 is a hydrocarbon radical having 1 to 20 carbon atoms, X is a halogen atom, and m is 0xe2x89xa6mxe2x89xa64;
[II] an organoaluminum compound represented by the general formula Al(OR3)pR4qX3-(p+q) wherein R3 and R4, which may be the same or different, are each a hydrocarbon residue having 1 to 24 carbon atoms, X is a halogen atom or hydrogen atom, and p and q are 0xe2x89xa6p less than 3, and 0xe2x89xa6qxe2x89xa63, provided 0 less than p+qxe2x89xa63; and
[III] a silicon compound represented by the general formula [R5aR6bR7cSi(OR8)dX4-(a+b+c+d)] where R5, R6, R7 and R8, which may be the same or different, are each a hydrocarbon residue having 1 to 20 carbon atoms, X is a halogen atom, and a, b, c and d are 0xe2x89xa6a less than 4, 0xe2x89xa6b less than 4, 0xe2x89xa6c less than 4 and 0 less than dxe2x89xa64, provided 0 less than a+b+c+dxe2x89xa64.
 less than 1 greater than Solid Catalyst Component
1. Component [I]
(1). The silicon oxide used in the present invention is silica or a double oxide of silicon and at least one another metal selected from Groups VII of the Periodic Table.
The aluminum oxide used as component (1) in the present invention is alumina or a double oxide of aluminum and at least one another metal selected from Group I to VIII in the Periodic Table.
As typical examples of the double oxide of silicon or aluminum and at least one another metal selected from Group VII in the Periodic Table there are mentioned various natural and synthetic double oxides such as Al2O3.MgO, Al2O3.CaO, Al2O3.SiO2, Al2O3.MgO.CaO, Al2O3.MgO.SiO2, Al2O3.CuO, Al2O3.Fe2O3, Al2O3.NiO, and SiO2.MgO. It is to be noted that these formulae are not molecular formulae but represent only compositions and that the structure and component ratio of the double oxide used in the present invention are not specially limited thereby. It goes without saying that the silicon oxide and/or aluminum oxide used in the present invention may have a small amount of water absorbed therein or may contain a small amount of impurities.
Although the properties of the silicon oxide and/or aluminum oxide used in the present invention are not specially limited so far as the objects of the present invention are not adversely affected thereby, a silica having a particle diameter of 1 to 200 xcexcm, an average pour volume of greater than 0.3 ml/g and a surface area of greater than 50 m2/g is preferred. Also, it is preferably calcined at 200-800xc2x0 C. prior to use.
(2). As the magnesium halide there is used a substantially anhydrous one. Examples are magnesium dihalides such as magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide, with magnesium chloride being particularly preferred.
These magnesium halides may have been treated with electron donors such as alcohols, esters, ketones, carboxylic acids, ethers, amines, and phosphines.
As examples of the compound of the general formula Me(OR)nXz-n used in the present invention wherein Me represents an element of Groups Ia to IVa in the Periodic Table, z represents the valence of the element Me, n is 0 less than nxe2x89xa6z, X is a halogen atom, and R is a hydrocarbon residue preferably radical, having 1 to 20, preferably 1 to 8, carbon atoms such as, for example, alkyl, aryl, or aralkyl, and Rs may be the same or different, there are mentioned compounds represented by NaOR, Mg(OR)2, Mg(OR)X, Ca(OR)2, Zn(OR)2, Cd(OR)2, B(OR)3, Al(OR)3, Al(OR)2X, Al(OR)X2, Si(OR)4, Si(OR)3X, Si(OR)2X2, Si(OR)X3, and Sn(OR)4. More concrete and preferred examples are Mg(OC2H5)2, Mg(OC2H5)Cl, Al(OCH3)3, Al(OC2H5)3, Al(On-C3H7)3, Al(Oi-C3H7)3, Al(On-C4H9)3, Al (Osec-C4H9)3, Al(Ot-C4H9)3, Al(OCH3)2Cl, Al(OC2H5)2Cl, Al(OC2H5)Cl2, Al(Oi-C3H7)2Cl, Al(Oi-C3H7)Cl2, Si(OC2H5)4, Si(OC2H5)3Cl, Si(OC2H5)2Cl2, Si(OC2H5)Cl3, Si(OCH2C6H5)4, B(OCH3)3, B(OC2H5)3, B(On-C4H9)3 and the like. It is preferable that the reaction ratio of the compound of the general formula Me(OR)nXz-n to the magnesium halide is in the range of 0.01 to 10, preferably 0.1 to 5 in terms of Me/Mg (molar ratio).
The method of reaction between the magnesium halide and the compound of the general formula Me(OR)nXz-n is not specially limited. There may be adopted a method in which both components are co-pulverized using, for example, ball mill, vibration mill, rod mill, or impact mill, at a temperature of 0xc2x0 to 200xc2x0 C., for 30 minutes to 50 hours, in the presence or absence of an inert hydrocarbon solvent. Or there may be adopted a method in which both components are mixed and reacted together under heating at a temperature of 20xc2x0 to 400xc2x0 C., preferably 50xc2x0 to 300xc2x0 C., for 5 minutes to 10 hours, in an organic solvent selected from inert hydrocarbons, alcohols, phenols, ethers, ketones, esters, nitriles and mixtures thereof, and thereafter the solvent is evaporated off. The method of co-pulverizing the two is preferred in the present invention.
(3). As examples of the titanium compound of the general formula Ti(OR1)mX4-m used in the present invention wherein R1 is a hydrocarbon radical having 1 to 20, preferably 1 to 12, carbon atoms such as an alkyl, aryl or aralkyl group, X is a halogen atom, and n is 0xe2x89xa6mxe2x89xa64, there are mentioned titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, monoethoxytrifluorotitanium, monoethoxytribromotitanium, diethoxydifluorotitanium, diethoxydichlorotitanium, diethoxydibromotitanium, triethoxyfluorotitanium, triethoxychlorotitanium, tetraethoxytitanium, monopropoxytrichlorotitanium, monoisopropoxytrichlorotitanium, dipropoxydichlorotitanium, diisopropoxydichlorotitanium, diisopropoxydibromotitanium, tripropoxyfluorotitanium, tripropoxychlorotitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, monoisobutoxytrichlorotitanium, dibutoxydichlorotitanium, diisopropoxydichlorotitanium, tributoxyfluorotitanium, tributoxychlorotitanium, triisobutoxychlorotitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetra-sec-butoxytitanium, tetra-tert-butoxytitanium, monopentyloxytrichlorotitanium, dipentyloxydichlorotitanium, tripentyloxymonochlorotitanium, tetra-n-pentyloxytitanium, tetra-cyclopentyloxytitanium, monooctyloxytrichlorotitanium, dioctyloxydichlorotitanium, trioctyloxymonochlorotitanium, tetra-n-hexyloxytitanium, tetra-cyclohexyloxytitanium, tetra-n-heptyloxytitanium, tetra-n-octyloxytitanium, mono-2-ethylhexyloxytrichlorotitanium, di-2-ethylhexyloxydichlorotitanium, tri-2-ethylhexyloxymonochlorotitanium, tetranonyloxytitanium, tetradecyloxytitanium, tetraisobornyloxytitanium, tetraoleyloxytitanium, tetraallyloxytitanium, tetrabenzyloxytitanium, tetrabenzhydryloxytitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxychlorotitanium, tri-o-xylenoxychlorotitanium, tetraphenoxytitanium, tetra-o-methylphenoxytitanium, tetra-m-methylphenoxytitanium, tetra-1-naphthyloxytitanium, tetra-2-naphthyloxytitanium and mixtures thereof. Among them, particularly, titanium tetrachloride, monoethoxytrichlorotitanium, diethoxydichlorotitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-n-hexyloxytitanium, tetra-n-octyloxytitanium and tetra-2-ethylhexyloxytitanium are preferred.
(4) The component [I] used in the present invention is prepared by reacting together (1) a silicon oxide and/or an aluminum oxide (component [I]-(1)), (2) a reaction product obtained by the reaction of a magnesium halide and a compound of the general formula Me(OR)nXz-n (component [I]-(2)) and (3) a titanium compound of the general formula Ti(OR1)mX4-m (component [I]-(3)) in the presence of a compound of the general formula R2OH.
Compounds of the general formula R2OH are those wherein R2 is a hydrocarbon radical having 1 to 20, preferably 6 to 12, carbon atoms, or an organic residue containing such an element as oxygen, nitrogen, sulfur, or chlorine. Preferred examples of such hydrocarbon radical are alkyl, alkenyl, aryl and aralkyl. Particularly preferred are those having a branch structure. As examples of the compound of the general formula R2OH there are mentioned 1-hexanol, 2-methyl-1-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-pentanol, 3-heptanol, 4-heptanol, 2,4-dimethyl-3-pentanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, 1-nonanol, 5-nonanol, 3,5-dimethyl-4-heptanol, 2,6-dimethyl-4-heptanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, 2,6,8-trimethyl-4-nonanol, 1-tridecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, phenol, chlorophenol, benzyl alcohol, methyl cellosolve, and mixtures thereof. Particularly, 2-methyl-1-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 2,4-dimethyl-3-pentanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, 3,5-dimethyl-4-heptanol, 2,6-dimethyl-4-heptanol and 3,5,5-trimethyl-1-hexanol are preferred.
It goes without saying that methanol commercially available as industrial grade alcohol or other modified alcohols such as hexane-modified alcohols may also be used without any trouble.
How to react the components [I]-(l) to [I]-(3) in the preparation of component [I] is not specially limited if only the reaction is conducted in the presence of a compound of the general formula R2OH. These components may be reacted with one another in any of the following orders:
(A) Components [I]-(l) to [I]-(3) are contacted at a time.
(B) Components [I]-(1) and [I]-(2) are contacted together, followed by contact with component [I]-(3).
(C) Components [I]-(1) and [I]-(3) are contacted together, followed by contact with component [I]-(2).
(D) Components [I]-(2) and [I]-(3) are contacted together, followed by contact with component [I]-(1). The above method (D) is preferred. More preferably, components [I]-(2) and [I]-(3) are dissolved and contacted together in advance, using a compound of the general formula R2OH as a solvent, followed by contact with component [I]-(1). In what order the components [I]-(2) and [I]-(3) should be dissolved in the compound of the general formula R2OH is not specially limited. Both may be dissolved at a time, or one may precedes the other.
There also may be adopted the following method. Component [I]-(2) and/or component [I]-(3) are (is) dissolved beforehand in a compound smaller in the number of carbon atom than the compound of the general formula R2OH, namely a compound having 1 to 5 carbon atoms, which is a so-called lower alcohol, and thereafter the components to be reacted are contacted together using the lower alcohol solution containing the component [I]-(2) and/or the component [I]-(3) and in the presence of the compound of the general formula R2OH.
According to a preferred method of contacting the components [I]-(1) to [I]-(3), these components are contacted, mixed and reacted in accordance with any of the foregoing contacting orders at a temperature of 20-300xc2x0 C., preferably 50-150xc2x0 C., for 1 minute to 48 hours, preferably 1 to 5 hours, in the presence of a compound of the general formula R2OH, and thereafter the compound of the general formula R2OH is removed by the reduction of pressure and/or heating.
As to the reaction ratio of the components, it is desirable to react the components [I]-(1) and [I]-(2) in such a manner that the magnesium content in the component [I]-(2) becomes 0.01 to 20 mmol, preferably 0.1 to 10 mmol, more preferably 0.2 to 4.0 mmol, per gram of the component [I]-(1). As to the components [I]-(1) and [I]-(3), it is preferable that the reaction be carried out using 0.01-10.0 mmol, preferably 0.1-5.0 mmol, more preferably 0.2-2.0 mmol, of component [I]-(3) per gram of component [I]-(1), although this ratio differs depending on whether the component [I]-(1) is subjected to a calcining treatment or not or conditions for the calcining treatment if applied.
As to the amount of the compound of the general formula R2OH to be used, it is desirable to use this compound in an amount of 0.1 to 50 g, preferably 1 to 30 g, per gram of component [I]-(2).
2. Component [II]
As examples of the organoaluminum compound of the general formula Al(OR3)pR4qX3-(p+q) used in the present invention wherein R3 and R4, which may be the same or different, are each a hydrocarbon residue preferably radical, having 1 to 24, preferably 1 to 12, carbon atoms, X is a halogen atom or hydrogen atom, and p and q are 0xe2x89xa6p less than 3 and 0xe2x89xa6qxe2x89xa63, provided 0 less than p+qxe2x89xa63 are dimethylaluminum methoxide, dimethylaluminum ethoxide, dimethylaluminum isopropoxide, dimethylaluminum t-butoxide, dimethylaluminum n-butoxide, dimethylaluminum sec-butoxide, diethylaluminum methoxide, diethylaluminum ethoxide, diethylaluminum isopropoxide, diethylaluminum n-butoxide, diethylaluminum sec-butoxide, diethylaluminum cyclohexyloxide, diethylaluminum t-butoxide, dipropylaluminum ethoxide, dipropylaluminum t-butoxide, dibutylaluminum t-butoxide, di-i-butylaluminum methoxide, di-i-butylaluminum ethoxide, di-i-butylaluminum isopropoxide, di-i-butylaluminum i-butoxide, di-i-butylaluminum t-butoxide, di-t-butylaluminum ethoxide, di-t-butylaluminum t-butoxide, dimethylaluminum phenoxide, di-n-hexylaluminum ethoxide, di-n-hexylaluminum isopropoxide, ethylethoxyaluminum chloride, isobutylethoxyaluminum chloride, ethylphenoxyaluminum chloride, phenylethoxyaluminum chloride, ethylethoxyaluminum hydride, ethylmethoxyaluminum chloride, ethylisopropoxyaluminum chloride, ethylbutoxyaluminum chloride, phenylaluminum dichloride, diphenylaluminum chloride, benzylaluminum dichloride, dibenzylaluminum chloride, dimethylaluminum chloride, diethylaluminum fluoride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, di-isobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and mixtures. Particularly, diethylaluminum chloride, ethylaluminum sesquichloride and ethylaluminum dichloride are preferred.
3. Component [III]
As the compound represented by the general formula [R5aR6bR7cSi(OR8)dX4-(a+b+c+d)] there may be used those wherein R5, R6, R7 and R8, which may be the same or different, are each a hydrocarbon radical having 1 to 20 carbon atoms, preferably 1-12 carbon atoms, such as hydrocarbon radical such as alkyl, aryl or aralkyl, X is hydrogen atom or a halogen atom such as chloro, bromo or iodo, and a, b, c and d are 0xe2x89xa6a less than 4, 0xe2x89xa6b less than 4, 0xe2x89xa6c less than 4 and 0 less than dxe2x89xa64, provided 0 less than a+b+c+dxe2x89xa64.
Examples of the silicon compound include various compounds represented by Si(OR8)4, Si(OR8)3X, Si(OR8)2X2, Si(OR8)X3, R5Si(OR8)3, R5Si(OR8)2X, R5Si(OR8)X2, R5R6Si(OR8)2, R5R6Si(OR8)X, R5R6R7Si(OR8) and the like. Concrete examples are Si(OCH3)4, Si(OC2H5)4, Si(Oi-C3H7)4, Si(On-C4H9)4, Si(OCH3)3Cl, Si(OC2H5)3Cl, Si(Oi-C3H7)3Cl, Si(On-C4H9)3Cl, Si(Osec-C4H9)3Cl, Si(OCH3)2Cl2, Si(OC2H5)2Cl2, Si(Oi-C3H7)2Cl2, Si(On-C4H9)2Cl2, Si(OC8H17)2Cl2, Si(OCH3)Cl3, Si(OC2H5)Cl3, Si(Oi-C3H7)Cl3, Si(On-C4H9)Cl3, Si(OC5H11)Cl3, Si(OC8H17)Cl3, Si(OC18H37)Cl3, Si(OC6H5)Cl3, Si(Op-CH3C6H5)Cl3, CH3Si(OCH3)3, CH3Si(OC2H5)3, CH3Si(Oi-C3H7)3, C2H5Si(OCH3)3, C2H5Si(OC2H5)3, C2H5Si(Oi-C3H7)3, i-C3H7Si(OCH3)3, i-C3H7Si(OC2H5)3, i-C3H7Si(Oi-C3H7)3, n-C3H7Si(OCH3)3, n-C3H7Si(OC2H5)3, n-C3H7Si(Oi-C3H7)3, n-C4H9Si(OCH3)3, n-C4H9Si(OC2H5)3, i-C4H9Si(OCH3)3, i-C4H9Si(OC2H5)3, t-C4H9Si(OCH3)3, t-C4H9Si(OC2H5)3, 
CH3Si(OCH3)2Cl, CH3Si(OC2H5)2Cl, CH3Si(Oi-C3H7)2Cl, CH3Si(OCH3)2Br, CH3Si(OC2H5)Br, CH3Si(Oi-C3H7)2Br, CH3Si(OCH3)2I, CH3Si(OC2H5)2I, CH3Si(Oi-C3H7)2I, C2H5Si(OCH3)2Cl, C2H5Si(OC2H5)2Cl, C2H5Si(Oi-C3H7)2Cl, C2H5Si(OCH3)2Br, C2H5Si(OC2H5)2Br, C2H5Si(Oi-C3H7)2Br, C2H5Si(OCH3)2I, C2H5Si(OC2H5)2l I, C2H5Si(Oi-C3H7)2I, i-C3H7Si(OCH3)2Cl, i-C3H7Si(OC2H5)2Cl, i-C3H7Si(Oi-C3H7)2Cl, n-C3H7Si(OCH3)2Cl, n-C3H7Si(OC2H5)2Cl, n-C3H7Si(Oi-C3H7)2Cl, n-C4H9Si(OCH3)2Cl, n-C4H9Si(OC2H5)2Cl, n-C4H9Si(Oi-C3H7)2Cl, i-C4H9Si(OCH3)2Cl, i-C4H9Si(OC2H5)2Cl, i-C4H9Si(Oi-C3H7)2Cl, t-C4H9Si(OCH3)2Cl, t-C4H9Si(OC2H5)2Cl, t-C4H9Si(Oi-C3H7)2Cl, 
CH3Si(OCH3)Cl2, CH3Si(OC2H5)Cl2, CH3Si(Oi-C3H7)Cl2, C2H5Si(OCH3)Cl2, C2H5Si(C2H5)Cl2, C2H5Si(Oi-C3H7)Cl2, i-C3H7Si(OCH3)Cl2, i-C3H7Si(OC2H5)Cl2, n-C3H7Si(OCH3)Cl2, n-C3H7Si(OC2H5)Cl2, n-C4H9Si(OCH3)Cl2, n-C4H9Si(OC2H5)Cl2, i-C4H9Si(OCH3)Cl2, i-C4H9Si(OC2H5)Cl2, t-C4H9Si(OCH3)Cl2, t-C4H9Si(OC2H5)Cl2, 
(CH3)2Si(OCH3)2, (CH3)2Si(OC2H5)2, (C2H5)2Si(OCH3)2, (C2H5)2Si(OC2H5)2, (i-C3H7)2Si(OCH3)2, (i-C3H7)2Si(OC2H5)2, (n-C3H7)2Si(OCH3)2, (n-C3H7)2Si(OC2H5)2, (n-C4H7)2Si(OCH3)2, (n-C4H9)2Si(OC2H5)2, (i-C4H9)2Si(OCH3)2, (i-C4H9)2Si(OC2H5)2, (t-C4H9)2Si(OCH3)2, (t-C4H9)2Si(OC2H5)2, 
(CH3)(C2H5)Si(OCH3)2, (CH3)(C2H5)Si(OC2H5)2, (CH3)(i-C3 7)Si(OCH3)2, (CH3)(i-C3H7)Si(OC2H5)2, (CH3)(t-C4H9)Si(OCH3)2, (CH3)(t-C4H9)Si(OC2H5)2, 
(C2H5)(i-C3H7)Si(OCH3)2, (C2H5)(i-C3H7)Si(OC2H5)2, (C2H5)(t-C4H9)Si(OCH3)2, (C2H5)(t-C4H9)Si(OC2H5)2, 
(CH3)2Si(Oi-C3H7)2, (C2H5)2Si(Oi-C3H7)2, (i-C3H7)2Si(Oi-C3H7)2, (t-C4H9)2Si(Oi-C3H7)2, 
(CH3)2Si(OCH3)Cl, (CH3)2Si(OC2H5)Cl, (C2H5)2Si(OCH3)Cl, (C2H5)2Si(OC2H5)Cl, (i-C3H7)2Si(OCH3)Cl, (i-C3H7)2Si(OC2H5)Cl, (t-C4H9)2Si(OCH3)Cl, (t-C4H9)2Si(OC2H5)Cl, 
(CH3) (t-C4H9)Si(OCH3)Cl, (CH3)(t-C4H9)Si(OC2H5)Cl, 
(CH3)2Si(Oi-C3H7)Cl, (C2H5)2Si(Oi-C3H7)Cl, 
(CH3)(t-C4H9)Si(Oi-C3H7)Cl, 
(CH3)3Si(OCH3), (CH3)3Si(OC2H5), (C2H5)3Si(OCH3), (C2H5)3Si(OC2H5), (CH3)2(t-C4H9)Si(OCH3), (CH3)2(t-C4H9)Si(OC2H5), 
and the like. Among them, Si(OCH3)4, Si(OC2H5)4, Si(OCH3)3Cl, Si(OC2H5)3Cl, Si(OCH3)2Cl2, Si(OC2H5)2Cl2, (CH2)Si (OCH3)2Cl, (C2H5)Si(OC2H5)2Cl, (CH3)2Si(OCH3)2, (C2H5)2Si(OC5H5)2, 
are most preferred.
4. Preparation of Solid Catalyst Component
The solid catalyst component used in the present invention is obtained by reacting the components [I] to [III] in any of the following orders:
(A) The components [I] and [II] are reacted at first, and then the component [III] is reacted with the above product.
(B) The components [I] and [III] are reacted at first, and then the component [II] is reacted with the above product.
(C) The components [II] and [III] are reacted at first, and then the component [I] is reacted with the above product.
(D) The components [I] to [III] are reacted at a time.
Reaction methods are not specially limited. For example, according to a preferred method, components to be reacted are contacted at a temperature of 0xc2x0 to 300+ C., preferably 20xc2x0 to 150xc2x0 C., for 5 minutes to 10 hours, in the presence or absence of an inert hydrocarbon solvent inert to conventional Ziegler catalysts, such as, for example, pentane, hexane, cyclohexane, heptane, octane, nonane, decane, benzene, toluene, or xylene. When the reaction is conducted in an inert hydrocarbon solvent, the solvent is preferably removed followed by the second stage reaction which may be conducted in the absence of any solvent or in the presence of a newly added solvent. Also, it is possible that the inert solvent is not removed after the first stage reaction, followed by the second stage reaction in the remaining solvent. Also, it is possible that the first stage reaction is conducted in the absence by evaporation or the like after the reaction. Of course, when the components [I], [II] and [III] are reacted stepwise in the manner as the above (A), (B) and (C), the first and/or second stage reaction may be conducted in the presence or absence of an inert hydrocarbon solvent. For example, the first stage reaction is conducted in an inert hydrocarbon solvent, and then the solvent is removed, of an inert solvent, followed by the second stage reaction in the absence of any solvent or in the presence of a newly added solvent.
As to the reaction ratio of the components [I], [II] and [III], the component [II] is preferably used in such a manner that the component [II]/{the component [I]-(3) in the component [I]} (molar ratio) is 0.01 to 100, more preferably 0.2 to 10, most preferably 0.5 to 5.0. The component [III] is preferably used in such a manner that the component [III]/{the component [I]-(3) in the component [I]} (molar ratio) is 0.01 to 10, more preferably 0.03 to 5.0, most preferably 0.05 to 1.0.
Of course, the reactions for the preparation of each component and the solid catalyst component should be performed in an inert gas atmosphere, and moisture should be avoided.
 less than 2 greater than  Organometallic Compound
The catalyst used in the present invention comprises the above mentioned solid catalyst component and an organometallic compound.
As the organometallic compound used in the present invention, there may be preferably employed an organometallic compound of a metal of Groups I-IV in the Periodic Table which is known as a component of Ziegler type catalyst. Particularly preferred are organoaluminum compounds and organozinc compounds. To illustrate these compounds, mention may be made of organoaluminum compounds of the general formulae R3Al, R2AlX, RAlX2, R2AlOR, RAl(OR)X and R3Al2X3 wherein R, which may be the same or different, is an alkyl or aryl group having 1 to 20 carbon atoms and X is a halogen atom, as well as organozinc compounds of the general formula R2Zn wherein R, which may be the same or different, is an alkyl group having 1 to 20 carbon atoms. Concrete examples are trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof.
The amount of the organometallic compound used is not specially limited. But usually it is in the range of 0.1 to 1,000 moles per mole of the titanium compound.
It is also preferable in the present invention that the organometallic compound component be used as a mixture or addition compound of the organometallic compound and an organic acid ester.
Where the organometallic compound component is used as a mixture of the organometallic compound and an organic acid ester, the organic acid ester is used usually in an amount of 0.1 to 1 mole, preferably 0.2 to 0.5 mole, per mole of the organometallic compound. Where it is used as an addition compound of the organometallic compound and the organic acid ester, the molar ratio is preferably in the range of 2:1 to 1:2.
The organic acid ester is the ester of a saturated or unsaturated, mono- or dibasic organic carboxylic acid having 1 to 24 carbon atoms and an alcohol having 1 to 30 carbon atoms. Examples are methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate, iso-propyl benzoate, butyl benzoate, hexyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoic acid-4-tolyl, methyl salicylate, ethyl salicylate, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, phenyl salicylate, cyclohexyl p-hydroxybenzoate, benzyl salicylate, ethyl xcex1-resorcinol carboxylate methyl anisate, methyl p-ethoxybenzoate, methyl p-toluylate, ethyl p-toluylate, phenyl p-toluylate, ethyl o-toluylate, ethyl m-toluylate, methyl p-aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, methyl naphthoate, and ethyl naphthoate.
Particularly preferred are alkyl esters, especially methyl esters, of benzoic acid, o- or p-toluic acid and anisic acid.
 less than 3 greater than  Polymerization of Olefin
The olefin polymerization using the catalyst of the present invention can be performed in the form of slurry polymerization, solution polymerization or vapor phase polymerization. The catalyst used in the present invention is particularly suitable for vapor phase polymerization. The polymerization reaction is carried out in the same way as in the conventional olefin polymerization reaction using a Ziegler type catalyst. More particularly, the reaction is performed in a substantially oxygen- and water-free condition in the presence or absence of an inert hydrocarbon. Olefin polymerizing conditions involve temperatures in the range of 20xc2x0 to 120xc2x0 C., preferably 50xc2x0 to 100xc2x0 C., and pressures in the range of atmospheric pressure to 70 kg/cm2, preferably 2 to 60 kg/cm2. Adjustment of the molecular weight can be done to some extent by changing polymerization conditions such as the polymerization temperature and the catalyst mole ratio, but the addition of hydrogen into the polymerization system is more effective for this purpose. Of course, using the catalyst of the present invention, there can be performed two or more multi-stage polymerization reactions involving different polymerization conditions such as different hydrogen concentrations and different polymerization temperatures.
The process of the present invention is applicable to the polymerization of all olefins that can be polymerized using a Ziegler type catalyst, preferably xcex1-olefins having 2 to 12 carbon atoms. For example, it is suitable for the homopolymerization of such xcex1-olefins as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene and the copolymerization of ethylene and an xcex1-olefin having 3-12 carbon atoms such as propylene, 1-butene, 1-hexene and 4-methylpentene-1, the copolymerization of propylene and 1-butene and the copolymerization of ethylene and one or more xcex1-olefins.
Copolymerization with dienes is also preferable for the modification of polyolefins. Examples of diene compounds which may be used for this purpose are butadiene, 1,4-hexadiene, ethylidene norbornene and dicyclopentadiene. The comonomer content in the copolymerization may be selected optionally. For instance, when ethylene and a xcex1-olefin having 3-12 carbon atoms is copolymerized, the xcex1-olefin content in the copolymer is preferably 0-40 molar %, more preferably 0-30 molar %.
 less than Effects of the Invention greater than 
Homopolymers or copolymers of olefins prepared by using as catalyst the solid catalyst component and the organometallic compound in the present invention are remarkably high in bulk density, relatively large in average particle diameter and narrow in particle size distribution and have a reduced proportion of fine particles, so there is little adhesion of polymer to the reactor walls during polymerization thus permitting stable operations. Besides, not only dusting can be prevented in a forming operation and so the efficiency of the forming operation can be enhanced, but also it is possible to omit a pelletizing step.
Further, since the homopolymers or copolymers in question according to the present invention are narrow in molecular weight distribution, they can be formed into films having high strength and superior in transparency and also superior in anti-blocking property and heat-sealability.